Linear-Structure Single-Atom Gold(I) Catalyst for Dehydrogenative Coupling of Organosilanes with Alcohols.

A strategy for the synthesis of a gold-based single-atom catalyst (SAC) via a one-step room temperature reduction of Au(III) salt and stabilization of Au(I) ions on nitrile-functionalized graphene (cyanographene; G-CN) is described. The graphene-supported G(CN)-Au catalyst exhibits a unique linear structure of the Au(I) active sites promoting a multistep mode of action in dehydrogenative coupling of organosilanes with alcohols under mild reaction conditions as proven by advanced XPS, XAFS, XANES, and EPR techniques along with DFT calculations. The linear structure being perfectly accessible toward the reactant molecules and the cyanographene-induced charge transfer resulting in the exclusive Au(I) valence state contribute to the superior efficiency of the emerging two-dimensional SAC. The developed G(CN)-Au SAC, despite its low metal loading (ca. 0.6 wt %), appear to be the most efficient catalyst for Si-H bond activation with a turnover frequency of up to 139,494 h-1 and high selectivities, significantly overcoming all reported homogeneous gold catalysts. Moreover, it can be easily prepared in a multigram batch scale, is recyclable, and works well toward more than 40 organosilanes. This work opens the door for applications of SACs with a linear structure of the active site for advanced catalytic applications.

Reactive Deposition Versus Strong Electrostatic Adsorption (SEA): A Key to Highly Active Single Atom Co-Catalysts in Photocatalytic H2 Generation.

In recent years, the use of single atoms (SAs) has become of a rapidly increasing significance in photocatalytic H2 generation; here SA noble metals (mainly Pt SAs) can act as highly effective co-catalysts. The classic strategy to decorate oxide semiconductor surfaces with maximally dispersed SAs relies on "strong electrostatic adsorption" (SEA) of suitable noble metal complexes. In the case of TiO2 - the classic benchmark photocatalyst - SEA calls for adsorption of cationic Pt complexes such as [(NH3 )4 Pt]2+ which then are thermally reacted to surface-bound SAs. While SEA is widely used in literature, in the present work it is shown by a direct comparison that reactive attachment based on the reductive anchoring of SAs, e.g., from hexachloroplatinic(IV) acid (H2 PtCl6 ) leads directly to SAs in a configuration with a significantly higher specific activity than SAs deposited with SEA - and this at a significantly lower Pt loading and without any thermal post-deposition treatments. Overall, the work demonstrates that the reactive deposition strategy is superior to the classic SEA concept as it provides a direct electronically well-connected SA-anchoring and thus leads to highly active single-atom sites in photocatalysis.

Light-Induced Migration of Spin Defects in TiO2 Nanosystems and their Contribution to the H2 Evolution Catalysis from Water.

The photocatalytic activity for H2 production from water, without presence of hole scavengers, of thermally reduced TiO2 nanoparticles (H-500, H-700) and neat anatase were followed by in-situ continuous-wave light-induced electron paramagnetic resonance technique (CW-LEPR), in order to correlate the H2 evolution rates with the electronic fingerprints of the photoexcited systems. Under UV irradiation, photoexcited electrons moved from the deep lattice towards the superficially exposed Ti sites. These photogenerated redox sites mediated (e- +h+ ) recombination and were the crucial electronic factor affecting catalysis. In the best-performant system (H-500), a synergic combination of mobile electrons was observed, which dynamically created diverse types of Ti3+ sites, including interstitial Ti3+ , and singly ionized electrons trapped in oxygen vacancies (VO . ). The interplay of these species fed successfully surface exposed Ti4+ sites, which became a catalytically active, fast reacting Ti4+ ⇄Ti3+ state that was key for the H2 evolution process.

Carbon Dots Detect Water-to-Ice Phase Transition and Act as Alcohol Sensors via Fluorescence Turn-Off/On Mechanism.

Highly fluorescent carbon nanoparticles called carbon dots (CDs) have been the focus of intense research due to their simple chemical synthesis, nontoxic nature, and broad application potential including optoelectronics, photocatalysis, biomedicine, and energy-related technologies. Although a detailed elucidation of the mechanism of their photoluminescence (PL) remains an unmet challenge, the CDs exhibit robust, reproducible, and environment-sensitive PL signals, enabling us to monitor selected chemical phenomena including phase transitions or detection of ultralow concentrations of molecular species in solution. Herein, we report the PL turn-off/on behavior of aqueous CDs allowing the reversible monitoring of the water-ice phase transition. The bright PL attributable to molecular fluorophores present on the CD surface was quenched by changing the liquid aqueous environment to solid phase (ice). Based on light-induced electron paramagnetic resonance (LEPR) measurements and density functional theory (DFT) calculations, the proposed kinetic model assuming the presence of charge-separated trap states rationalized the observed sensitivity of PL lifetimes to the environment. Importantly, the PL quenching induced by freezing could be suppressed by adding a small amount of alcohols. This was attributed to a high tendency of alcohol to increase its concentration at the CD/solvent interface, as revealed by all-atom molecular dynamics simulations. Based on this behavior, a fluorescence "turn-on" alcohol sensor for exhaled breath condensate (EBC) analysis has been developed. This provided an easy method to detect alcohols among other common interferents in EBC with a low detection limit (100 ppm), which has a potential to become an inexpensive and noninvasive clinically useful diagnostic tool for early stage lung cancer screening.

Carboxylated Graphene for Radical-Assisted Ultra-Trace-Level Water Treatment and Noble Metal Recovery.

Sorption technologies, enabling removal of heavy metals, play a pivotal role in meeting the global demands for unrestricted access to drinking water. Standard sorption technologies suffer from limited efficiency related to the weak sorbent-metal interaction. Further challenges include the development of technologies enabling smart metal recovery and sorbent regeneration. To this end, a densely functionalized graphene, with 33% by mass content of carboxyl groups, linked through direct C-C bonds (graphene acid, GA) represents a previously unexplored solution to this challenge. GA revealed excellent efficiency for removal of highly toxic metals, such as Cd2+ and Pb2+. Due to its selective chemistry, GA can bind heavy metals with high affinity, even at concentrations of 1 mg L-1 and in the presence of competing ions of natural drinking water, and reduce them down to drinking water allowance levels of a few µg L-1. This is not only due to carboxyl groups but also due to the stable radical centers of the GA structure, enabling metal ion-radical interactions, as proved by EPR, XPS, and density functional theory calculations. GA offers full structural integrity during the highly acidic and basic treatment, which is exploited for noble metal recovery (Ga3+, In3+, Pd2+) and sorbent regeneration. Owing to these attributes, GA represents a fully reusable metal sorbent, applicable also in electrochemical energy technologies, as illustrated with a GA/Pt catalyst derived from Pt4+-contaminated water.

Microwave Energy Drives "On-Off-On" Spin-Switch Behavior in Nitrogen-Doped Graphene.

The established application of graphene in organic/inorganic spin-valve spintronic assemblies is as a spin-transport channel for spin-polarized electrons injected from ferromagnetic substrates. To generate and control spin injection without such substrates, the graphene backbone must be imprinted with spin-polarized states and itinerant-like spins. Computations suggest that such states should emerge in graphene derivatives incorporating pyridinic nitrogen. The synthesis and electronic properties of nitrogen-doped graphene (N content: 9.8%), featuring both localized spin centers and spin-containing sites with itinerant electron properties, are reported. This material exhibits spin-switch behavior (on-off-on) controlled by microwave irradiation at X-band frequency. This phenomenon may enable the creation of novel types of switches, filters, and spintronic devices using sp2 -only 2D systems.